Diffusion transfer photographic materials



United States Patent cc 3,352,678

Patented Nov. 14, 1967 3352 678 wherein R and R each represents lower alkyl, aryl,

aralkyl, an SO M-substituted alkyl, an SO M-substi- DIFFUSION TRANSFER PHOTOGRAPHIC tuted aryl, an SO M-substituted aralkyl, a COOM-sub- MATERIALS Fumihiko Nishio Odawanbshi, Kanagawwken and st tuted allryl, a COOM-substrtuted aryl, a COOM-su-b- Reiichi 0i and Tatsnya Tajima, Ashigarakami-gun, 5 stltuted y Whefe-M represents K r, Kanagawa-ken, Japan, assignors to Fuji Shashin an amino substituted alkyl, an amino substituted aryl, and Film Kabushiki Kaisha, Kanagawa-ken, Japan, a anamino substituted aralkyl; R and R together may corporation of Japan form a divalent alkylene radical and together with an No Drawing. Filed Sept. 24, 1963, Ser. No. 311,232

ad t 't (1 Claims p y application p Oct. 1962, 1acen n1 rogen atom may form a heterocychc ring, an

10 n is a positive integer less than 10.

14 Claims. 6 96 76) Examples represented by the above-mentioned general formula are as follows: The present invention relates to diffusion trans-fer COMPOUND 1 photographic materials such as a photographic light 15 cm,

sensitive element, a photographic image receiving element, and a developer for difiusion transfer photography,

which materials contain a novel toner. N 02H, A diliusion transfer photographic process means in .7 y

general a process comprising exposing a light sensitive element having a light sensitive layer of silver halide to COMPOUND 2 an object or an original image, in the presence of a 01H; developer, contacting said light sensitive element with S=C N CH2N an image receiving element having an image receiving I I Q layer containing reducing nuclei such as colloidal silver N or silver sulfide capable of reducing silver complex on the surface, whereby the silver halide at the exposed N portion of the photosensitive layer is developed and the CO N 3 silver halide at the unexposed portion is dissolved and CHr-CH: diffused, followed by depositing on the image-receiving layer as reduced silver, and separating it to obtain a I g printing image with the Objectn the image receiving N 2- 2 element. I

In the case where a toner having an eifect on the de- 7 position of reduced silver on the image receiving layer COMPOUND 4 is not used in the present photographic process, the re- GET-CH1 sulting image on the image-receiving layer is not black, S) but yellow or brown. OH OH The present invention relates to a process for forming Q N I r 2 a black image on the image-receiving layer by employ- 40 ing a novel toner which has not been described in the prior literatures. According to the present invention, a COMPOUND 5 compound represented by one of the following general 1500 H formulas is added as a toner into a sllver halide emulsion I B 7 layer, an image-receiving layer, or a developer, :or a com- 'S=C NQHT'N OHB N C=S bination of the said two or three materials, I I I I Y N\ N N /N R N N COMPOUND 7 wherein R is a member selected from the group consisting of a lower alkyl group, hydrogen and halogen; Y s=C N-CH2'N O(or)S is a member selected from the group consisting of I I CH2. QH:

era-@N N lh l \N% -N- d N-(CH nw an COMPOUND s CHr-CH:

3 COMPOUND 9 COMPOUND 10 SOzH (or Na, K, NH!) 2 s=ONCHr-I ICHsNC=8 l l ILQ A mixture of two or more toners may, of course, be used in the method of the present invention.

It is profitable to add these compounds in an amount of 0001-1 'g. per liter of a developer, 0.001-1 g. per kilogram of a silver halide emulsion, and, 0001-1 g. per liter of a solution for forming an image receiving element having an image-receiving layer, respectively. A binder of the silver halide emulsion layer, and the image-receiving layer may be gelatin or the like, or a mixture thereof.

Example I A extra-hard silver chloride emulsion was coated on a photographic paper to form a light sensitive element having the following composition:

G./m. Silver chloride 1.2 Benzotriazole 0.005 Hydroquinone 0.2 Gelatin 4.2

An original image to be copied was exposed on the dried emulsion layer and treated with a developer having the following composition:

Hydroquinone g 12 Pyrazone 1-phenyl-3-pyrazo1idone g 0.5 Sodium sulfite (anhydrous) g 70 Caustic soda g 15 water to make ...mL.. 1000 During or after development the emulsion layer of the light sensitive element containing the developer was closely in contact with the image-receiving layer of the image receiving element for about seconds. The image receiving element was a coated material on a paper support having the following composition:

Gelatin 5 Sodium thiosulfate (anhydrous) 1.5 Starch 0.5 Colloidal silver sulfide 0.002 0.05

Compound 1 By separating the image receiving emulsion layer fromv the light sensitive emulsion layer, a black positive image was obtained on the image receiving material.

Example 2 Benzotriazole in the light sensitive element employed in Example 1 was replaced with Compound 3 (0.01 g./m. In this case, even if Compound 1 in the image receiving element was removed, a black positive image was obtained by the same treatment as in Example 1, and stability of the light sensitive emulsion layer was, also, improved.

Example 3.

An, original image was exposed by reflection on the same light sensitive element as employed in Example 1, and treated with a developer having the following composition:

Hydroquinone g 18 Pyrazone 1-phenyl-3-pyrazolidone g 0.5 Compound 5 g 0.05 Sodium sulfite (anhydrous) g 60 Sodium thiosulfate (anhydrous) g 8 Sodium hydroxide g 14 Water to make -mL- 1000 By the same treatment as employed in Example 1, the light sensitive emulsion layer containing the developer was closely in contact with the image-receiving layer of the image receiving, material having the following composition. In this case, as a support for the image receiving material, paper or transparent base could be used.

I, (ix/111. Gelatin 4 Polyvinyl alcohol 1.5 Compound 7 0.06 Barium sulfate 0.4 Palladium sulfide colloid 0.003

When the image-receiving layer of the image receiving material was separated from the light sensitive emulsion layer a black image was obtained on the image-receiving layer of the image receiving material. In this case, scum on the surface of the image receiving image could be removed.

Example 4 provement comprising at least one toner having a formula selected from the group consisting of (A) El and wherein R represents a member selected from the group consisting of a lower alkyl group, hydrogen, and a halogen atom; Y represents a member selected from the group consisting of wherein R and R each represents lower alkyl, aryl, aralkyl, a --SO M-substituted alkyl, a sO M-substituted aryl, a So M-substituted aralkyl, a COOM-su'bstituted alkyl, a COOM-substituted aryl, a COOM-substituted aralkyl, where M represents H, Na, K, or NH an amino substituted alkyl, an amino substituted aryl, and an amino substituted aralkyl; and wherein R and R together may form a divalent alkylene radical and R and R together with an adjacent nitrogen atom may form a heterocyclic ring; and n is a positive integer less than 10.

2. A composition according to claim 1, wherein said first member is a light sensitive silver halide composition.

3. A composition according to claim 1, wherein said first member is an image receiving composition.

4. A composition according to claim 1, wherein said first member is a developer.

5. A composition according to claim 1, wherein R and R together with an adjacent nitrogen atom form a heterocyclic ring.

6. A composition according to claim 5, wherein said heterocyclic ring contains a member selected from the group consisting of oxygen and sulphur.

7. A composition according to claim 6, wherein the toner has the formula (A).

8. A composition according to claim 1, wherein t toner has the formula (B), and Y is CzHs 10. A composition according to claim 1, wherein the toner is CHz-CHz 11. A composition according to claim 1, wherein the 10 toner is 12. A composition according to claim 1, wherein the toner is 14. A composition according to claim 1, wherein the 35 toner is CHr-CHQ I I No references cited.

J. TRAVIS BROWN, Acting Primary Examiner.

NORMAN G. TORCHIN, Examiner.

C. E. DAVIS, Assistant Examiner. 

1. IN A DIFFUSION TRANSFER PHOTOGRAPHIC COMPOSITION CONTAINING A FIRST MEMBER SELECTED FROM THE GROUP CONSISTING OF A LIGHT SENSITIVE SILVER HALIDE COMPOSITION, AN IMAGE RECEIVING COMPOSITION, AND A DEVELOPER; THE IMPROVEMENT COMPRISING AT LEAST ONE TONER HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF F WHEREIN R REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A LOWER ALKYL GROUP, HYDROGEN, AND A HALOGEN ATOM; Y REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF 